EP0970984B1 - Perfluoropolyether-Acylperoxide und deren Herstellung - Google Patents

Perfluoropolyether-Acylperoxide und deren Herstellung Download PDF

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Publication number
EP0970984B1
EP0970984B1 EP99111117A EP99111117A EP0970984B1 EP 0970984 B1 EP0970984 B1 EP 0970984B1 EP 99111117 A EP99111117 A EP 99111117A EP 99111117 A EP99111117 A EP 99111117A EP 0970984 B1 EP0970984 B1 EP 0970984B1
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Prior art keywords
range
formula
process according
reaction
average molecular
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EP99111117A
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English (en)
French (fr)
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EP0970984A3 (de
EP0970984A2 (de
Inventor
Ivan Wlassics
Vito Tortelli
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Syensqo Specialty Polymers Italy SpA
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Solvay Solexis SpA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/324—Polymers modified by chemical after-treatment with inorganic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine

Definitions

  • the present invention relates to an improved process to obtain with high yields poly- and diacyl-peroxides of (per)-fluoropolyethers starting from the corresponding diacyl- and monoacyl-halides.
  • the reaction which can be carried out in batch in a stable peroxide dispersion in KOH/H 2 O 2 which contains the acylic halide, occurs in very short times, from few seconds to 30 seconds, under stirring such that the Reynolds number results in the range 1.000-40.000.
  • Fluorinated and non fluorinated organic solvents and surfactants can be added.
  • the reactions are generally carried out at 0°C but also at room temperature.
  • the contact time generally ranges, as said, from 1 to 30 seconds.
  • the process uses solvents having high ODP (e.g. CFCH 3 , CF 2 Cl-CFCl 2 ).
  • An object of the present invention is a process to obtain with improved yields (per)fluoroether acylperoxides having an average equivalent weight (EW) in the range 350-5.000, having formula: (I) Y' - (CF 2 -CF(CF 3 )O) m -(CX'FO) n -CF 2 CO-O-O-CO-CF 2 -(OCX'F) n - -(OCF(CF 3 )-CF2) m -Y' wherein
  • the process is carried out at a temperature comprised between -5°C and +5°C in a mixture formed by two immiscible liquid phases having a total volume equal to at most 2/3 of the reactor one, kept under stirring so that no emulsions are formed, said liquid phases being the following:
  • the ratio between the alkali moles and the -CO-Y" functional groups equivalents is comprised between 1.2 and 1.8 and the ratio between the aqueous phase ml volume and the base grams is comprised between 5 and 10; preferably the organic phase volume is half than that of the reactor.
  • the reactant addition is carried out in a time depending on the perfluoropolyether acylic halides of formula (I') and (II') MW and it ranges from 20 to 30 seconds for the perfluoropolyether acyclic halides having MW in the range 350-800 and it is lower than or equal to 15 seconds for those having a MW in the range 800-5.000.
  • the perfluoropolyethers of the polyhalogenated organic solvent have preferably number average molecular weight in the range 400-1.000.
  • the preferred solvents are perfluoro polyethers having perfluoroalkylic end groups.
  • the process object of the present invention is feasible in batch, and allows to obtain with high yields polyacylperoxide or diacylperoxide mixtures with EW in the range 350-5.000.
  • peroxides of formula (II) with equivalent weights (EW) between 1.000 and 2.000, starting from (per)fluoropolyether halides of formula (II') with number average molecular weight 1.000-2.000 are obtained.
  • reaction product mixtures obtainable starting from (II') the relative amounts of diacyl peroxides and polyacylperoxides are related to the hydrogen peroxide excess and, the conditions being equal, with the compound (II') molecular weight.
  • equivalent weight of the peroxide it is meant the equivalent weight calculated from the molecular weight of the starting acylhalide, subtracted the halogen atomic weight and added that of the oxygen.
  • the reaction yield is calculated by determining the titre in peroxides of the organic phase by titration with an aqueous titrated solution of sodium thiosulphate in the presence of a 50% w/v potassium iodide aqueous solution.
  • the total reaction time is determined from time to time by determining the acylhalide conversion percentage, which is obtained taking samples from the reaction mixture at different times, starting when the addition of the (per)fluoropolyether monoacyl or diacyl-halide of formula (I') or (II'), respectively, begins. More specifically the analysis is carried out by the quantitative FTIR technique, by monitoring the peak area decrease corresponding to the stretching of the compound of formula (I') or (II') acylic groups and determining the ratio with respect to the initial area, the compound weight being the same. The reaction is stopped when this ratio reaches the required value (75% conversion of (I') or (II') at t max ).
  • the invention process gives particularly high yields for the peroxides obtained from acylhalides (II') having number average molecular weight in the range 1.000-2.000.
  • the Applicant has unexpectedly found that starting from acylhalides having number average molecular weight in the range 350-3.000, the invention process allows to obtain with improved yields products wherein polyacylperoxides are in a higher concentration.
  • the invention process has been found applicable also to average molecular weights of the starting compounds higher than 2.000, up to 5.000, and the yields are industrially good and better than the processes of the art.
  • a further object of the invention consists in dipolyacylperoxides of formula (I) and (II).
  • the (per)fluorinated peroxides obtained by the process according to the present invention are used as chain initiators in (per)fluoroelastomer and thermoplastic polymerizations. These (per)fluorinated peroxides have chemical physical properties such as to result compatible with the polymerization system. Moreover the possibility to determine the half-life times of the peroxide homolitic decomposition on the basis of its equivalent weight allows to select the most suitable operating conditions for the polymerization.
  • the (per)fluoropolyether (di/poly)acyl peroxides can be used also as modifiers of non fluorinated polymers, such as polyacrylates, to give better surface properties, or as intermediates for agrochemical and pharmaceutical compounds.
  • the used equipment consists in a 200 ml glass flask having 4 ground necks equipped with nechanical blade stirrer, condenser, dropping funnel and thermometer. The equipment is assembled so that the flask can be dipped in a 2 l refrigerant bath and at a temperature between -40°C and -70°C.
  • Example 1 One proceeds as in Example 1. The addition time was 15 seconds while the t max was fixed at the time when the acylchloride conversion was 75%.
  • PFPE perfluoropolyether
  • Example 3 the solvent is Freon® 113 (high ODP).
  • Example 1 was repeated carrying out the reactant addition in a total time over the 20 seconds limit: 25 seconds in Example 4 and 300 seconds in Example 5.
  • Comparative example Addition time acylchloride (seconds) Yield No. 4 25 32% No. 5 300 6% In Example 4 the yields are 46% of those of Example 1, in Example 5 about 9%.
  • the poly-acylperoxide halflife (t 1/2 ) was determined with the following method. 16-17 g of the peroxide were dissolved in 150 ml of C 6 F 14 . 1.5 ml portions of this solution are distributed in test-tubes, which are then closed and thermostated at 20°C. Starting from the zero time (experiment beginning), and then at regular intervals, the peroxide quantitative determination is carried out by titration with thiosulphate, by using 5-6 different samples at a time and calculating an average value of the obtained titres. Then a graph is drawn, reporting in ordinates the solution concentration in g of peroxide/ml of solvent and in abscissas the time, expressed in minutes. In this way the t 1 / 2 at 20°C has been determined, which resulted of 4606 minutes.
  • the t 1/2 value determined with the above mentioned method was of 4500 minutes.
  • Example 6 was repeated changing the cooling system to allow ⁇ T thermal rises respectively below and over the +6 - +20°C limits.
  • the ⁇ T values were respectively 3°C, 26°C, 32°C (initial temperature 0°C).
  • the following comparative Examples 7-9 show that the previously mentioned thermal increase give rise to an yield decrease. Comparative Example Thermal rise (°C) Yield No. 7 +3 35% No. 8 + 26 40.2% No. 9 + 32 35% In particular from Example 7 it results that by cooling the system in reaction so that the temperature rise is of 5°C, the yields are half than those of Example 6.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyethers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Steroid Compounds (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Claims (10)

  1. Verfahren zur Herstellung von (Per)fluoretheracylperoxiden mit einem mittleren Äquivalentgewicht (EW) im Bereich von 350-5000 und den Formeln: (I)   Y'-(CF2-CF(CF3)O)m-(CX'FO)n-CF2CO-O-O-CO-CF2-
    (OCX'F)n-(OCF(CF3)-CF2)m-Y'        worin
       Y' = Cl, ORf, wobei Rf ein C1-C3-Perfluoralkyl ist;
       m, n solche ganze Zahlen sind, daß (I) das genannte EW ergibt, und m/n ≥ 40;
       X' = F, CF3; (II)   T-CF2-O-[(CF2CF2O)p-(CF2O)q-CF2-CO-O-O-CO-
    CF2(OCF2)q-(OCF2CF2)p]y-OCF2-COOH        worin
       y eine ganze Zahl zwischen 1 und 5 ist;
       p und q solche ganze Zahlen sind, daß sich das oben genannte EW ergibt, und p/q = 0,5 - 2,0;
       T = COOH, F, mit der Einschränkung, daß wenn T = COOH dann y = 1-5, wenn T = F dann y = 1;
    ausgehend von Perfluoretheracylhalogeniden mit einem Molekulargewicht-Zahlenmittel (MW) im Bereich von 350-5000 und den Formeln: (I')   Y'-(CF2-CF(CF3)O)m-(CX'FO)n-CF2CO-Y"    worin
       Y', X', m und n die für (I) angegebene Bedeutung haben;
       Y" = Cl, F;
       bzw. (II')   Y'''-CF2-O-(CF2CF2O)p-(CF2O)q-CF2-CO-Y"    worin
       Y" die für (I') angegebene Bedeutung hat;
       Y''' = CO-Y", F;
    durch Umsetzung mit H2O2 in basischem Milieu bei einer Temperatur im Bereich von -5°C - +5°C in einer aus zwei nicht mischbaren flüssigen Phasen gebildeten Mischung mit einem Gesamtvolumen von höchstens 2/3 von dem des Reaktors, die ständig gerührt wird, so daß sich keine Emulsionen bilden, wobei die flüssigen Phasen die folgenden sind:
    eine organische Phase, die aus einem perfluorierten Lösungsmittel gebildet ist, das ausgewählt ist aus linearen C6-C10-Perfluoralkanen, Perfluorpolyethern mit endständigen Perfluoralkylgruppen, die gegebenenfalls an einer oder beiden endständigen Gruppen ein Wasserstoffatom enthalten, in einer größeren Menge,
    eine wäßrige alkalische Lösung, die einen Überschuß, bezogen auf das zugegeben Halogenid, an Wasserstoffperoxid enthält;
    wobei das Verfahren die folgenden Schritte umfaßt:
    a) Zugabe eines (Per)fluorpolyethermonoacyl- oder -diacylhalogenids unter Kühlung, so daß der Temperaturanstieg ΔT, bezüglich eines Reaktors mit einem Innenvolumen im Bereich von 50 - 250 ml, der mit einem Tieftemperaturbad mit 2 l Volumen und einer Temperatur zwischen -40°C und -80°C gekühlt wird, im Bereich von 6°C - 20°C liegt, und daß die Temperatur nach Ende der Zugabe im Verlauf von 0,1 - 5 Minuten auf die Anfangstemperatur absinkt;
    b) Fortführen der Reaktion bei der Anfangstemperatur für die erforderliche Zeit (tmax), um eine 75%ige Umwandlung des Acylhalogenids der Formel (I') oder (II') zu erhalten, wobei die Umwandlung durch quantitative FTIR bestimmt wird;
    c) Abbruch der Reaktion, indem man das Rühren stoppt und die Phasen sich trennen läßt, wobei man das System auf der Anfangstemperatur hält, und anschließende Rückgewinnung der organischen Phase, die die Perfluorpolyetherdiacyl-/polyacylperoxide enthält.
  2. Verfahren nach Anspruch 1, wobei in Schritt a) das Verhältnis von Mol Alkali und Äquivalenten funktioneller -CO-Y"-Gruppen im Bereich von 1,2 - 1,8 liegt und das Verhältnis zwischen ml Volumen wäßrige Phase und Gramm Base im Bereich von 5 - 10 liegt und das Volumen der organischen Phase die Hälfte von dem des Reaktors beträgt.
  3. Verfahren nach Anspruch 1, wobei in Schritt a) die Reaktantenzugabe bei den Perfluorpolyetheracylhalogeniden (I') und (II') mit einem MW im Bereich von 350 - 800 im Verlauf von 20 bis 30 Sekunden erfolgt und bei solchen mit einem MW im Bereich von 800 - 5000 in weniger als oder gleich 15 Sekunden erfolgt.
  4. Verfahren nach den Ansprüchen 1-3, wobei die Perfluorpolyether ein Molekulargewicht-Zahlenmittel im Bereich von 400 - 1000 besitzen.
  5. Verfahren nach Anspruch 4, wobei das Lösungsmittel ein Perfluorpolyether ist.
  6. Verfahren nach den vorangehenden Ansprüchen 1-5, erhältlich chargenweise.
  7. Verfahren nach den Ansprüchen 1-6, wobei ausgehend von (Per)fluorpolyetherhalogeniden der Formel (II') mit einem Molekulargewicht-Zahlenmittel von 1000 - 2000 Acylperoxide der Formel (II) mit einem Äquivalentgewicht (EW) im Bereich von 1000 - 2000 erhalten werden.
  8. Verfahren nach den Ansprüchen 1-6, wobei ausgehend von Halogeniden der Formel (I') mit einem Molekulargewicht-Zahlenmittel von 350 - 800 Diacylperoxide der Formel (I) mit einem Äquivalentgewicht von 350 bis 800 erhalten werden.
  9. Verfahren nach den Ansprüchen 1-6, wobei mit Halogeniden der Formel (II') mit einem MW im Bereich von 3000 - 5000 Diacylperoxide der Formel (II) mit y = 1 erhalten werden; bei einem Molekulargewicht-Zahlenmittel im Bereich von 350 - 3000 Polyacylperoxidmischungen erhalten werden und in der Formel (II) y = 1-5 und T = COOH.
  10. Acylperoxide der Formeln (I) und (II) nach Anspruch 1.
EP99111117A 1998-06-11 1999-06-08 Perfluoropolyether-Acylperoxide und deren Herstellung Expired - Lifetime EP0970984B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT1998MI001328A IT1301684B1 (it) 1998-06-11 1998-06-11 Acilperossidi perfluoropolieterei e procedimento per il loroottenimento.
ITMI981328 1998-06-11

Publications (3)

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EP0970984A2 EP0970984A2 (de) 2000-01-12
EP0970984A3 EP0970984A3 (de) 2001-04-11
EP0970984B1 true EP0970984B1 (de) 2003-05-02

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US (1) US6187894B1 (de)
EP (1) EP0970984B1 (de)
JP (1) JP4499210B2 (de)
DE (1) DE69907323T2 (de)
IT (1) IT1301684B1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090163692A1 (en) * 2007-12-21 2009-06-25 General Electric Company Aromatic polyethers
WO2010117029A1 (ja) * 2009-04-08 2010-10-14 旭硝子株式会社 ペルフルオロ有機過酸化物の製造方法
EP3623440B1 (de) * 2017-05-12 2026-01-14 Daikin Industries, Ltd. Oberflächenbehandlungsmittel mit perfluor(poly)ethergruppenhaltiger verbindung
KR20220034026A (ko) * 2019-07-12 2022-03-17 에이지씨 가부시키가이샤 퍼플루오로아실 과산화물의 제조 방법 및 플루오로알킬아이오다이드의 제조 방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2559630A (en) * 1950-03-04 1951-07-10 Du Pont Fluorinated acyl peroxides
US3461155A (en) * 1965-01-18 1969-08-12 Minnesota Mining & Mfg Bis(omega-substituted perfluoroacyl) peroxides
US5021516A (en) * 1989-06-26 1991-06-04 E. I. Du Pont De Nemours And Company Poly(perfluoroether)acyl peroxides
JPH0768210B2 (ja) * 1989-06-27 1995-07-26 日本油脂株式会社 ポリフルオロアルカノイルペルオキシド
JPH05170731A (ja) * 1991-12-24 1993-07-09 Nippon Oil & Fats Co Ltd ペルフルオロ−オキサ−アルカノイルハライド及び過酸化ジペルフルオロ−オキサ−アルカノイル
JPH07138362A (ja) * 1993-11-19 1995-05-30 Nippon Oil & Fats Co Ltd 含フッ素ポリメリックペルオキシド、その製造方法及びそれを用いたフルオロアルキル基含有重合体
US5831131A (en) * 1995-08-30 1998-11-03 E. I. Du Pont De Nemours And Company Process for preparing peroxides

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Publication number Publication date
ITMI981328A1 (it) 1999-12-13
EP0970984A3 (de) 2001-04-11
JP2000007779A (ja) 2000-01-11
US6187894B1 (en) 2001-02-13
DE69907323T2 (de) 2004-05-13
EP0970984A2 (de) 2000-01-12
JP4499210B2 (ja) 2010-07-07
IT1301684B1 (it) 2000-07-07
DE69907323D1 (de) 2003-06-05

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